To increase electrolysis performance, the applicability of seawater to the iron-fed electro-Fenton process was considered. Three kinds of graphite electrodes (activated carbon fiber-ACF, carbon felt, graphite) and dimensionally stable anode (DSA) electrode were used to select a cathode having excellent hydrogen peroxide generation and organic decomposition ability. The concentration of hydrogen peroxide produced by ACF was 11.2 mg/L and those of DSA, graphite, and carbon felt cathodes were 12.9 ~ 13.9 mg/L. In consideration of durability, the DSA electrode was selected as the cathode. The optimum current density was found to be 0.11 A/cm2, the optimal Fe2+ dose was 10 mg/L, and the optimal ratio of Fe2+ dose and hydrogen peroxide was determined to be 1:1. The optimum air supply for hydrogen peroxide production and Rhodamine B (RhB) degradation was determined to be 1 L/min. The electro-Fenton process of adding iron salt to the electrolysis reaction may be shown to be more advantageous for RhB degradation than when using iron electrode to produce hydrogen peroxide and iron ion, or electro-Fenton reaction with DSA electrode after generating iron ions using an iron electrode.